Recording method

ABSTRACT

A recording method comprising forming a metallic image on a dielectric film base, then generating electric charge on the film base by friction electrification, and simultaneously applying toner material having the inverse polarity to that of the electric charge on the electrified film base.

United States Patent 119 Hashiue et a1.

[5 RECORDING METHOD [75] Inventors: Masakazu Hashiue; Hiroyuki Ueda;

Satoru Honio; Shingo Ooue, all of Asaka, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22 Filed: Oct.22, 1970 21 Appl. No.: 83,007

[30] Foreign Application Priority Data Oct. 22, 1969 Japan 44-84543 [52] US. Cl. 117/37 LE, 96/1 LY, 96/1.4, 117/93, 117/107 [51'] Int. Cl G03g 13/10 [58] Field of Search 117/37 LE, 17.5, 93, 107; l18/DIG. 23; 355/10; 96/1 LY, 1.3, 1 SD, 1.4

[56] References Cited UNITED STATES PATENTS 1,784,912 12/1930 Scott 117/17.5 2,297,691

10/1942 Carlson 117/17.5

111 1 3,821,011 1451 June 28,1974

2,681,473 Carlson 117/17.5

6/1954 3,056,881 10/1962 Schwarz 346/76 3,119,707 -1/l964 'Christs 346/76 3,123,564 3/1964 Oliphant .11 252/62.1 3,132,963 5/1964 Jarvis. 117/17.5 3,314,073 I 4/1967 Becker 346/76 3,518,081 6/1970 Bickmore et a1. 117/] 7.5

FOREIGN PATENTS OR APPLICATIONS 1,085,573 10/1967 Great Britain 1l7/|7.5

Primary Examiner-Michael Sofocleous Attorney, Agent, or Firm-J. T. Martin; Gerald J. Ferguson, Jr.;'Joseph J. Baker 57 ABSTRACT A recording method comprising'forming a metallic image on a dielectric film base,'then generating electric charge on the film base by friction electrification, and simultaneously applying toner material having the inverse polarity to that of the electric charge on the electrified film base.

8 Claims, 1 Drawing Figure 1 RECORDING METHOD This invention relates to a recording method comprising forming metallic image on a support surface and applying toner on the metallic image.

According to the conventional copying process using the electronic photography, the photoconductive material layer is uniformly electrified by the corona dis charge,.the optical image is projected on said electrified material layer to form the distribution of electric charge corresponding to the optical image, and then the layer is subjected to the cascade developing and the toner is printed on the printing paper sheet.

An apparatus for executing this copying process requires the instruments for the uniform electrification of the photoconductive layer, and therefore the copying apparatus becomes intricate and the electrifying treat ment requires considerable long time. Besides, the cascade developing has such defect that the image is hard to be reproduced due to the edge effect.

According to the process of this invention, the uniform electrification prior to the cascade developing is not necessary, and therefore much time is saved and the reproduction of the image is easily made.

On the other hand, a conventional copyingmethod described in British Pat. No. 1,085,573, which comprises exposing the polyester film or Kodakphotoresist to the ultraviolet ray to change the friction electrification characteristics, then rubbing the film with suitable material and developing the film with the cascade developing agent, has such defect that the image is not made by the visible ray and the rubbing ofthe film must be done prior to the developing. Whereas, the method of this invention is able to form the image by means of the visible ray, the ultraviolet ray and the electron beam, and besides is able to achieve simultaneously the friction of electrification and the developing treatment.

Another conventional copying method described in US. Pat. No. 3,133,963 which comprises electrifying uniformly the back face of processed silver salt film, exposing the film to the infrared ray, and developing the exposed back face with the toner to obtain the image corresponding to the deposited Ag picture, has such defects that the troublesome electrifying and infrared ray exposing treatments are required and the quality of the picture is much fallen since the toner image corre sponding to the Ag picture is obtained through a film base having definite thickness. Whereas, according to the method of this invention characterized by forming the thin metallic image in the film base surface and forming the toner image on the same surface, the distinction of the printed image is satisfactory.

The method of this invention will be explained more particularly.

The metallic image is first formed on the surface of the dielectric base body, then electric charge is generated on the surface by rubbing the surface with the cascade developing agent or by shaking the dielectric base in a liquid developer and simultaneously the toner material having the inverse polarity to that of the electric charge is sticked to the electrified surface. By printing the toner image on the other sheet, the printed image corresponding to the metallic image can be obtained. Many sheets of the same printed image can be obtained by repeating a series of steps of the rubbing or shaking electrification of the base film having the metallic image, the application of the toner material to the base film and the printing of the toner image on the other sheet. Therefore, once the metallic image has been formed on the dielectric film base, pluralities of the same image can be obtained successively and at any time by means of the simple apparatus without electrification and exposing of the film.

The favorable dielectric base film is made from a film of cellulose triacetate, cellulose diacetate, cellulose ac: etate or polyethylene terephthalate film having the ordinary photographic undercoating layer, or the film of the organic polymer of said compounds having the surface resistance of more than 10"0 fl Suitable metal for forming the metallic image is Ag, Al, Cr, Cu, or other ordinary metals.

Method of producing the metallic image may be any one of following treatments (I) (5).

1. developing a thin film of vacuum-deposited Ag halide. I I l 2. etching chemically or peeling mechanically desired zone of the vacuum-deposited uniform metal layer.

3. evaporating the desired zone of the vacuumdeposited uniform metal layer with the electron beam, electric discharge or laser.

4. vacuum-depositing or sputtering highly heated metal by means of a mask.

' 5. drawing with electrically conductive paint containing metal powder. r

The toner image sticked to the printing negative film can be printed, ormay be used as it is. In the case of projecting with the reflecting light, the contrast of the projected image is much increased by using the negative film carrying the toner picture.

Therefore, the uniform electrification and the exposing of the film base are not required every time when one sheet of the copy is made because the toner is sticked to the dielectric film base as corresponding to the metallic image thereon by only rubbing the film base with the cascade-developing agent or shaking the same in a liquid developer using the simple structure apparatus. Besides, the metallic image on the film base can be preserved for long time to be used again at any timelater.

The printing of the optical image may be conducted by the optical focalizing, the contact penetration printing, or the contact reflection printing.

The'optical image may be also drawn on an electron sensitive material by means of an electron beam.

Now, some examples of this invention will be described with reference to an accompanied drawing showing a series of steps of the printing method.

Example 1 Ag bromide layer2 was first vacuum-deposited on a cellulose triacetate film 1 having the under coating layer produced by'dispersing gelatin in cellulose nitrate. Then, the desired optical image was printed on the obtained deposited film, which was subjected to the photographical treatments under following conditions.

Developing; dipped in the commercial developing solu- Papitol (produced by Fuji Photo Film Co., Ltd.) at 20C in 0.5 2 seconds.

Stopping; dipped in a solution composed of glacial acetic acid l5 cc and water 1,000 cc at 20C in 2 seconds.

Fixing; dipped in the commercial fixing solution Super Fuji Fix (produced by Fuji Photo Film Co., Ltd.) at 20C in seconds.

Washing with water; washed with flowing water in seconds.

Thus, a negative Ag image 3 was formed on the undercoating layer of the cellulose triacetate film corresponding to the optical image. The obtained film 4 having the surface metallic image was designated hereinafter as printed negative.

By rubbing the printed negative with the cascade developing agent, the toner 5 was sticked to the surface of the printed negative. The amount of the toner sticked to the surface zone without Ag image were more than that sticked to the surface zone with the Ag image. As the cascade developing agent, that for the electrophotographic copying apparatus Xerox 914 was used. Then, the toner image 5 sticked to the printed negative was printed electrostatically on a printing paper sheet 7 by corona discharging means 6. After that, the printed paper sheet 7 carrying the toner 8 was heated or exposed to the vapor of the solvent to fix the toner picture 9. By rubbing again the printed negative with the cascade developing agent, the toner can be also sticked to the printed negative. The toner image was then printed on the printing paper sheet and the printed sheet was fixed. After a series of these cascade developing, printing and fixing steps were repeated 200 times, no significant degradation of the printed image was observed, as far as it was visually inspected. One of the merits of this method is to be able to obtain a positive printed image by exposing the positive optical image.

Example 2 developing; in D72"* (l 2) solution at 20C in 40 seconds. stopping; in a solution composed of glacial acetic acid cc and water 1000 cu in 30 seconds. fixing:

in Super Fuji Fix" at C in 2 minutes.

the composition of the D72 solution.

metol 3.0 g anhydrous sodium sulfite 45.0 g hydroquinone 12.0 g Sodium carhonntc( Na CO;,'H- ,O) 81.9 Potasinm bromide 2.0 water to make l000 ml.

Then the gelatine on the Ag image zone was removed according to the etch-bleach method characterized by dipping the processed film into a mixed solution composed of following A and B solutions.

Composition of A Solution H 0 750 cc CuSO,- 5 H 0 120 g citric acid 150 g -Continued Composition of A Solution KBr 7.5 g Water to make I000 ml.

' B Solution H 0 37 aq. solution The higher the photographic concentration of the Ag image, the more amount of gelatine were decomposed and removed. After that, the film was dipped in caustic soda 20 wt. percent aq. solution in 40 sec., and the Al vacuum-deposited Al layer was dissolved and removed. The amount of Al removed corresponded to that existed on the exposed image. The film was further dipped in warm water at about C to remove residual gelatine, and washed with water and dried. As this result, the vacuum-deposited Al layer corresponding to the exposed optical image was formed, ie the printed negative as designated in the Example 1 was obtained. Many printed sheets of the same image were obtained by repeating the step of cascade-developing of the printed negative, the step of printing the toner image and the step of fixing the toner image.

Example 3 Metallic Al was vacuum-deposited on a cellulose triacetate film or polyethylene terephthalate film, and letters or pictures were painted on the Al deposited layer with 20 percent caustic soda solution in atmospheric air. Thus, the Al parts painted with the NaOH solution were dissolved, and the resultant film was washed with water and dried to obtain the printed negative. Then, i

the cascade developing, toner printing and fixing steps were repeated in the similar manner as in the Example 1, and pluralities of printedv sheets having the same image were obtained.

In the above described three examples, the printed negative obtained by treating the film produced by vacuum-deposited Ag halide layer on the ordinary photographic film base is able to exhibit the continuous tone relatively easily and to produce the high quality printed picture.

It will be understood to those skilled in the art that the method of this invention will not be restricted only to the examples but various modifications will be made without departing from the spirit and scope of this invention as described in the appended claim.

What is claimed is:

1. A recording method comprising forming a metallic image on a dielectric film base, then generating electric charge on said film base by friction electrification, and simultaneously applying toner material having the in verse polarity to that of the electric charge on said electrified film base.

2. A recording method as claimed in claim 1 wherein the step of applying toner material comprises rubbing said film base with a cascade developer containing carrier beads and toner.

3. A recording method as claimed in claim 1 wherein the step of applying toner material comprises shaking said film base in a liquid developer containing an electrically insulating liquid and toner.

4. A recording method as claimed in claim 1 wherein the metallic image is formed by photographically developing a vacuum-deposited film of silver halide on the surface of the film base.

7. A recording method as claimed in claim 1 wherein the metallic image is formed by evaporating the desired zone of a vacuum-deposited uniform metal layer on said dielectric film base with the electron beam, electric discharge or laser.

8. A recording method as claimed in claim 1 wherein said dielectric film base is substantially transparent. 

2. A recording method as claimed in claim 1 wherein the step of applying toner material comprises rubbing said film base with a cascade developer containing carrier beads and toner.
 3. A recording method as claimed in claim 1 wherein the step of applying toner material comprises shaking said film base in a liquid developer containing an electrically insulating liquid and toner.
 4. A recording method as claimed in claim 1 wherein the metallic image is formed by photographically developing a vacuum-deposited film of silver halide on the surface of the film base.
 5. A recording method as claimed in claim 2 wherein the metallic image is formed by photographically developing a vacuum-deposited film of silver halide on the surface of the film base.
 6. A recording method as claimed in claim 3 wherein the metallic image is formed by photographically developing a vacuum-deposited film of silver halide on the surface of a film base.
 7. A recording method as claimed in claim 1 wherein the metallic image is formed by evaporating the desired zone of a vacuum-deposited uniform metal layer on said dielectric film base with the electron beam, electric discharge or laser.
 8. A recording method as claimed in claim 1 wherein said dielectric film base is substantially transparent. 